Deep groundwater flow and geochemical processes in limestone aquifers: evidence from thermal waters in Derbyshire, England, UK

Thermal waters potentially provide information on geochemical processes acting deep within aquifers. New isotopic data on groundwater sulphate, inorganic carbon and strontium in thermal and non-thermal waters of a major limestone aquifer system in Derbyshire, England, UK, are used to constrain sulphate sources and groundwater evolution. Shallow groundwaters gain sulphate from oxidation of sulphide minerals and have relatively ¹³C-depleted dissolved inorganic carbon (DIC). Thermal waters have relatively high Sr/Ca and more ¹³C-enriched DIC as a result of increased water–rock interaction. In other respects, the thermal waters define two distinct groups. Thermal waters rising at Buxton have higher Mg, Mn and ⁸⁷Sr/⁸⁶Sr and lower Ca and SO₄, indicating flow from deep sandstone aquifers via a high permeability pathway in the limestone. By contrast, Matlock-type waters (97% of the thermal flux) have elevated sulphate concentrations derived from interaction with buried evaporites, with no chemical evidence for flow below the limestone. About 5% of the limestone area's groundwater flows to the Matlock group springs via deep regional flow and the remainder flows via local shallow paths to many non-thermal springs. Gypsum dissolution has produced significant tertiary porosity and tertiary permeability in the carbonate aquifer and this is an essential precursor to the development of karstic drainage.